JP5906888B2 - Glass frit and crystallized glass - Google Patents

Glass frit and crystallized glass Download PDF

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JP5906888B2
JP5906888B2 JP2012076670A JP2012076670A JP5906888B2 JP 5906888 B2 JP5906888 B2 JP 5906888B2 JP 2012076670 A JP2012076670 A JP 2012076670A JP 2012076670 A JP2012076670 A JP 2012076670A JP 5906888 B2 JP5906888 B2 JP 5906888B2
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linear expansion
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章弘 菱沼
章弘 菱沼
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旭硝子株式会社
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Description

The present invention is an SiO 2 —B 2 O 3 —MgO—Al 2 O 3 -based glass composition that does not contain an alkali component and is suitable for sealing or bonding between inorganic members. The present invention relates to a composition and a sealing material made therefrom.

  In the manufacture of a composite member made of a metal material, a ceramic material, or the like, there is a method in which a sealing material containing a glass composition as a main component is fired to form a fired body, and these materials are sealed or bonded together. At this time, as the sealing material, glass powder (also referred to as glass frit) produced by pulverizing a glass composition, press frit produced from the glass frit, and the like are widely used.

  On the other hand, when the sealing part is exposed to a high temperature as represented by a chemical reactor sealing material of solid oxide fuel cells (hereinafter referred to as SOFC), a conventional glass composition is used. When the sealing material produced from the above was used, the fired body was softened and deformed at a high temperature, and sufficient sealing could not be performed.

  Patent Document 1 proposes the use of a glass composition made of borosilicate as a SOFC sealing material to obtain a thermally stable fired body. However, boric acid contained in the glass composition is likely to cause corrosion of the sealing material, and at the working temperature of 700 to 1000 ° C., the problem of maintaining the fluidity and shape of the sealing portion is sufficient. It was not solved.

  Patent Documents 2 and 3 describe a glass composition in which a fired body having high thermal stability can be obtained by precipitating crystals when the glass component does not contain boric acid or is contained in a small amount when it is made into a fired body. Has been proposed. Then, it has been proposed to use the proposed glass composition in the form of a glass frit or glass paste for a sealing material in a portion exposed to a high temperature.

  However, since the glass composition of Patent Document 2 contains a large amount of alkali metal oxide, the alkali metal component diffuses in the fired body in a high working temperature range, for example, the operating temperature range of the SOFC, The fluidity of the sealing part has not been sufficiently solved.

Patent Document 3 discloses that the glass composition is mol% based on oxide, and SiO 2 35 to 41.5%, MgO 8 to 25%, CaO more than 27% and 35% or less, SrO 0 to 2%, BaO. 0 to 4%, ZnO 5 to 15%, Al 2 O 3 4.5 to 10%, and the content of these components is 97% or more of the whole, and if SrO and BaO are contained, those contents A lead-free glass composition having a total amount of 2% or less has been proposed. When sealing using the sealing material produced from this glass composition, the sealing temperature became as high as 900-1100 degreeC, and there existed a problem of the damage of the sealing material by a heat | fever.

Patent Document 4, the glass composition, in weight percent on the oxide basis, SiO 2 10~30%, B 2 O 3 20~30%, CaO10~40%, 15~40% MgO, SrO + BaO + ZnO 0~10% Al 2 O 3 0-5%, La 2 O 3 0-5%, RO 2 (R is Zr, Ti or Sn) 0-3% Alkali-free glass is proposed. In the proposed glass, the sealing temperature can be lowered to 900 ± 50 ° C., and since crystals are precipitated when fired, corrosion of the sealing material can be suppressed even if it contains boric acid.

However, since the glass composition described in Patent Document 4 contains a large amount of CaO, crystals such as β-CaSiO 3 (α = 60 to 70 × 10 −7 / ° C.) having a low linear expansion coefficient are locally precipitated. It is an easy-to-use composition system. These crystals may cause cracks at the sealing interface in sealing a sealing material having a high linear expansion coefficient.

Japanese Patent No. 3681821 JP 2010-184826 A International Publication No. 2009/17173 Pamphlet JP 2007-161568 A

  In view of the above problems, the present invention is a glass composition that does not contain an alkali metal and has a low CaO content, crystals with a low coefficient of linear expansion do not precipitate in firing, and the fired body has excellent heat resistance. It aims at providing the glass composition which shows this.

  And if a sealing material is sealed using the sealing material produced from the glass composition of this invention, the glass composition which a crack does not generate | occur | produce in a sealing interface and does not corrode a sealing material will be provided. With the goal.

  Furthermore, it aims at providing the glass frit produced from the said glass composition as a sealing material, the glass paste produced from the said glass frit, a press frit, and a green sheet.

As a result of repeated studies to solve the above-mentioned problems, the present inventors have adjusted the content of the components of the SiO 2 —B 2 O 3 —MgO—Al 2 O 3 -based glass composition. By firing the glass powder of the glass composition at a temperature of less than 900 ° C., crystals having a high linear expansion coefficient are precipitated in the fired body, and the linear expansion coefficient of the fired body is 90 to 135 × 10 −7 / ° C. I found it.

That is, the present invention substantially does not contain an alkali metal oxide, and is expressed in mass% in terms of oxide,
SiO 2 2~30% by weight,
B 2 O 3 10 to 30 wt%,
MgO 5 to 35% by mass,
Exceeding 10% by mass exceeding Al 2 O 3 0,
ZnO 0-25% by mass,
BaO 0-30% by mass,
La 2 O 3 6~45 wt%,
MO 2 Less than six weight% (M is Ce, Sn, 1 or more elements selected from the group consisting of Zr and Ti), and contains, from the glass composition characterized by containing no CaO substantially A glass frit is provided.

Moreover, this invention provides the following sealing materials produced from the said glass composition.
A glass frit produced by pulverizing the glass composition of the present invention.
A fired body obtained by firing the glass frit of the present invention.
A glass paste produced by mixing the glass frit of the present invention with an organic vehicle or the like.
A press frit produced by press-molding the glass frit of the present invention and firing it at a temperature equal to or higher than the softening point of the glass.
A green sheet produced by mixing the glass frit of the present invention and an organic vehicle, etc., applying the mixture to a transparent resin film, and drying.

According to the glass composition of the present invention, the glass powder prepared by pulverizing the glass composition exhibits good fluidity during firing, and crystallized glass in which crystals having a high linear expansion coefficient are precipitated upon firing. Thus, a fired body having a high linear expansion coefficient is obtained. Therefore, the sealing material produced from the glass powder can be used for sealing a sealing material having a high linear expansion coefficient, and the sealing portion can be used in a high-temperature atmosphere in a temperature range of 600 to 1000 ° C. It does not deform and exhibits excellent heat resistance. Furthermore, since an alkali component is not contained in the glass composition, deterioration due to diffusion of the alkali component to the sealing material does not occur even when exposed to a temperature range of 600 to 1000 ° C. during and after sealing. Furthermore, since the contents of B 2 O 3 and CaO are appropriately adjusted, corrosion of the sealing material and generation of cracks at the sealing interface can be suppressed.

  Since the glass composition of the present invention has the above properties, the glass frit made of the glass composition and the glass paste, press frit and green sheet produced from the glass frit are suitable as a sealing material for SOFC. Since there is no risk of a decrease in viscosity at high temperatures, the insulation of the seal part and the durability of the seal can be improved.

Relationship between total amount of MgO + ZnO + La 2 O 3 (mol%) and bending degree When clear bending is observed in the linear expansion curve of the fired body of Example 1 When no clear bending is observed in the linear expansion curve of the fired body of Example 6

  The glass composition of the present invention is prepared by preparing glass materials, mixing, melting, and rapidly cooling. The melting temperature is usually 1400 to 1500 ° C., but is appropriately adjusted depending on the glass composition. And normally, the glass composition of this invention is grind | pulverized to make glass powder, the glass powder is baked, and it uses for sealing of an inorganic material as a baked body. A ball mill or the like can be used for the pulverization.

  When the powder of the glass composition of the present invention is fired, it is preferable that a crystal phase is precipitated in the fired body at a firing temperature of less than 900 ° C. The firing time is preferably 60 to 120 minutes. The firing temperature is not particularly limited, but it is preferably as low as possible in order to prevent damage to the sealing material due to heat. Therefore, the firing temperature is more preferably 870 ° C. or less, and further preferably 850 ° C. or less. On the other hand, although the lower limit is not particularly set, when the firing temperature is low, the flowability of the glass powder is low, the wettability with the sealing material is low, and the sealing force is weakened. Furthermore, it becomes difficult to produce crystals, and the function of the present invention may be impaired. Therefore, the firing temperature is preferably 780 ° C. or higher, more preferably 800 ° C. or higher.

  The temperature raising process of the firing temperature is not particularly limited. For example, it is maintained at a temperature lower than the firing temperature to generate crystal nuclei, and then heated to the firing temperature and held at the firing temperature to grow the nuclei and precipitate as crystals. It is preferable to use crystallized glass. The temperature lower than the firing temperature is a temperature at which the nucleation rate is high, and is typically obtained using a differential thermal analysis curve (hereinafter referred to as a DTA curve) of glass.

  When the glass powder produced from the glass composition of the present invention is fired and sealed, the glass powder shrinks, comes into contact with the sealing material while softening and flowing, and when cooled, the sealing material and the fired body. And unite. Therefore, it is preferable that the glass powder has high fluidity when the temperature is increased. When the fluidity is low, a gap is formed between the fired body and the sealed object after firing, and a sufficient sealing force cannot be obtained. The fluidity of the glass powder can be evaluated by, for example, the flow button method. In the flow button method, a sample (flow button) having a diameter of 1 cm is produced by press-molding 1.5 g of glass powder, and the temperature of the sample is raised and the shape change is evaluated. In order to obtain a good sealing force, a fluidity that causes roundness in the short part of the cylinder is preferable, and a fluidity that cannot maintain the cylindrical shape is more preferable.

  The average particle size of the glass powder is preferably 5 to 50 μm. The said particle size can be adjusted with the conditions of a grinding | pulverization. When the average particle size is less than 5 μm, the glass is likely to be crystallized, which is a factor that hinders the fluidity of the glass, which is not preferable in sealing the sealing material. On the other hand, when the average particle size exceeds 50 μm, the crystallization speed is slow, and the reaction with the sealing material may be accelerated, which is not preferable. In the present specification, the average particle size of the glass powder refers to a value measured using a laser diffraction / scattering particle size analyzer.

  The fired body (crystallized glass) obtained by firing the glass powder produced from the glass composition of the present invention preferably has 50% by volume or more crystallized, and 70% by volume or more is crystallized. It is more preferable because the stability and shape maintaining characteristics of the sealing part at high temperatures can be exhibited.

The fired body preferably has an average coefficient of linear expansion (α) at 50 to 800 ° C. of 90 to 135 × 10 −7 / ° C. And 100-130 * 10 < -7 > / degreeC is more preferable, and 110-125 * 10 < -7 > / degreeC is further more preferable. If it is less than 90 × 10 −7 / ° C., it becomes difficult to match the linear expansion coefficients when used while being bonded to the sealing material, and the reliability of sealing may be lowered.

Therefore, it is preferable that crystals having a linear expansion coefficient higher than 70 × 10 −7 / ° C. precipitate on the fired body. Examples of crystals having such a high linear expansion coefficient include BaO—ZnO—SiO 2 based crystals (α = about 90 to 110 × 10 −7 / ° C.) such as BaZnSiO 4 , forsterite (Mg 2 SiO 6 ). MgO—SiO 2 crystal (α = about 90 to 120 × 10 −7 / ° C.), BaO—MgO—SiO 2 crystal such as BaMgSiO 4 , MgO—B such as suanite (Mg 2 B 2 O 5 ) Examples include 2 O 3 based crystals and La 2 O 3 —B 2 O 3 based crystals such as LaBO 3 . Among these, at least one of the MgO—B 2 O 3 -based crystal and the La 2 O 3 —B 2 O 3 -based crystal is preferable from the viewpoint that the transformation of the crystal at the firing temperature is small and the sealing strength after firing is maintained. More preferably, it is mainly present.

On the other hand, the precipitation of crystals having a low linear expansion coefficient causes cracks at the sealing interface, so it is preferable that they do not precipitate. For example, a CaO—BaO crystal, a CaO—SiO 2 crystal (α = 60 to 70 × 10 −7 / ° C.), a ZnO—SiO 2 crystal (α = 30 to 40 × 10 −7 / ° C.), or a BaO -Al 2 O 3 -SiO 2 based crystal (α = 30~40 × 10 -7 / ℃) and the like. However, in the scope of the present invention, the BaO—Al 2 O 3 —SiO 2 crystal also precipitates a phase having a high linear expansion coefficient such as hexacelsian (α = 80 to 90 × 10 −7 / ° C.), Some precipitation is allowed.

Further, it is preferable that the fired body not only has a linear expansion coefficient in the above-mentioned range, but also has a curve indicating the expansion rate of the linear expansion coefficient with respect to a temperature change (hereinafter referred to as a linear expansion curve) having no inflection point. Furthermore, it is preferable that the degree of bending (unit: 10 −7 / ° C.) of the linear expansion curve is small. It gets closer to a straight line as it gets smaller. In the present specification, the bending degree refers to a value calculated as follows.

As shown in FIG. 2, when a clear bend is observed in the linear expansion curve, the difference in linear expansion coefficient at two points at 50 ° C. before and after the bent point is defined as the degree of bending. On the other hand, as shown in FIG. 3, when no clear bending is observed in the linear expansion curve, the linear expansion coefficient is calculated from the linear expansion curve every 100 ° C. at 300 to 1000 ° C. The maximum value of the coefficient difference is defined as the degree of bending. In calculating the degree of bending, the linear expansion coefficient is calculated with 50 ° C. as a reference. The degree of bending of the linear expansion curve is an index of the content of non-crystallized glass (hereinafter referred to as amorphous glass) in the fired body, and an index indicating the magnitude of instantaneous volume change during the temperature rising and falling process. It becomes. That is, when the degree of bending is large, the amorphous glass content is high, so that the structure of the fired body becomes weak and cracks are likely to occur at the sealing interface when sealing a sealing material having a high linear expansion coefficient. . Also, cracks are likely to occur in the fired body or in the sealing interface due to momentary elongation or contraction during the temperature raising and lowering process. Therefore, an inflection point does not occur in the linear expansion curve, and the bending degree is preferably 13 × 10 −7 / ° C. or less, and the bending degree is more preferably 10 × 10 −7 / ° C. or less, and 5 × 10 −7 / ° C. The following is more preferable.

  The yield temperature of the fired body is preferably 900 ° C. or higher. If it is bent below 900 ° C., the structure of the sealed portion cannot be maintained and may be deformed, which is not preferable. Therefore, More preferably, it is 920 degreeC or more, More preferably, it is 940 degreeC or more.

Next, the component of the glass composition of this invention is demonstrated below.
SiO 2 is a component that forms the glass skeleton of the glass composition, is a main component of a silicate crystal that gives a high linear expansion coefficient in a fired body by firing, and is an essential component. The content of SiO 2 is 2 to 30% by mass. If it is less than 2% by mass, vitrification becomes difficult during the production of the glass composition. Further, crystals are produced during the production of the glass composition, and the fluidity during the firing of the glass powder is lowered. If it exceeds 30% by mass, the rate at which crystals precipitate is reduced, and the rate of crystal formation (hereinafter referred to as crystallinity) decreases. Further, the glass transition point becomes too high, and the fluidity is lowered. And the preferable range of content is 3-27 mass%, More preferably, it is 4-25 mass%.

B 2 O 3 is a component that forms the glass skeleton of the glass composition, is a main component of borate crystals that gives a high linear expansion coefficient in the fired body by firing, and is an essential component. The content of B 2 O 3 is 10 to 30 mass%. If it is less than 10% by mass, crystals are produced during production of the glass composition, and desired fluidity cannot be obtained during firing. On the other hand, if it exceeds 30% by mass, the degree of crystallinity during firing becomes low, and the degree of bending of the linear expansion curve of the fired body becomes large. In addition, an interfacial reaction may proceed with the material to be sealed before crystal deposition during firing, which may reduce the reliability of sealing. The preferable range of the content is 12 to 27% by mass, and more preferably 14 to 25% by mass.

  MgO is a component that facilitates the precipitation of crystals when the glass powder is fired, and is an essential component. The content of MgO is 5 to 35% by mass. If it is less than 5% by mass, the amount of crystals deposited is small and the crystallinity is lowered. Therefore, the linear expansion coefficient of the fired body is lowered, and the heat resistance of the sealing portion at high temperature is lowered. On the other hand, if it exceeds 35 mass%, the glass becomes unstable during the production of the glass composition. In addition, since the crystallization start temperature becomes too low and the speed of crystal precipitation is remarkably increased, it becomes easier to crystallize at a lower temperature. Thereby, the fluidity | liquidity at the time of baking of glass powder falls, and favorable sealing property cannot be obtained. The preferable range of the content is 7 to 30% by mass, and more preferably 10 to 27% by mass.

Al 2 O 3 is a component that increases the chemical durability of the glass composition and the sealing material, and further increases the sealing power with the sealing material, and is an essential component. The content of Al 2 O 3 is more than 0 and 10% by mass or less. If Al 2 O 3 is not substantially contained, the glass becomes unstable in the production of the glass composition, and the powder of the glass composition does not exhibit the desired fluidity during firing. If it exceeds 10% by mass, a large amount of BaO—Al 2 O 3 —SiO 2 crystal having a low linear expansion coefficient or a volume change due to phase transition between 300 to 400 ° C. is precipitated in the fired body. The linear expansion coefficient cannot be obtained. The preferable range of the content is 1.5 to 9% by mass, and more preferably 2 to 8.5% by mass.

ZnO is a component that enhances the fluidity of the glass powder at a low temperature and facilitates the precipitation of crystals during firing, and is not an essential component. The content of ZnO is 0 to 25% by mass. If it exceeds 25% by mass, there is a possibility that willemite having a low linear expansion coefficient is precipitated, and the chemical durability, particularly acid resistance, of the fired product is lowered. Therefore, the content is preferably 1 to 24% by mass, and more preferably 2 to 23% by mass. Moreover, when containing ZnO, it is preferable to contain BaO or CaO simultaneously. By simultaneously containing BaO or CaO, the precipitation of low linear expansion coefficient willemite can be suppressed, and RO-ZnO-SiO 2 (R is Ba, Ca, etc.) based crystals having a high linear expansion coefficient are further precipitated.

CaO is a component that facilitates precipitation of crystals during firing, and is not an essential component. The content of CaO is 0 to 9% by mass. CaO is also the main component of crystals with a low linear expansion coefficient. When the content exceeds 10% by mass and the amount of precipitated crystals with a low linear expansion coefficient increases, cracks occur at the sealing interface with the sealing material. Cause. Therefore, the content is preferably 1 to 8% by mass, and more preferably 2 to 5% by mass. Furthermore, CaCO 3 often used as a raw material for CaO has a large volatilization amount of carbon dioxide gas in the melting of the glass raw material, and a phenomenon called carry-over in which the raw material powder volatilizes on the exhaust gas flow easily occurs. There is a risk of causing quality degradation such as compositional deviation accompanying volatilization of components.

  BaO is a constituent component of the silicate crystal that gives a high linear expansion coefficient, and is a component used to adjust the linear expansion coefficient of the fired body, but is not an essential component. For example, when the coefficient of linear expansion is increased, the content is increased, and when it is decreased, the content is decreased. The content of BaO is 0 to 30% by mass. If it exceeds 30% by mass, the degree of crystallinity will be low, causing cracks in the fired product. The content is preferably 1 to 27 mass%, more preferably 5 to 25 mass%.

La 2 O 3 is a constituent component of a borate crystal that gives a high linear expansion coefficient, and is a component used to adjust the linear expansion coefficient of the fired body, but is not an essential component. Moreover, it is a component which raises a crystallinity degree and can make a bending degree small in a linear expansion curve. The content of La 2 O 3 is 0 to 45% by mass. If it exceeds 45 mass%, the glass becomes unstable during the production of the glass composition, and the fluidity of the glass powder decreases during firing. The content is preferably 6 to 43% by mass, and more preferably 10 to 40% by mass.

MO 2 (M is one or more elements selected from the group consisting of Ce, Sn, Zr and Ti) is a component that increases the chemical durability of the glass and increases the crystallinity during firing, but is not an essential component. . Then, MO 2 is the total amount 6% by mass (CeO 2 + SnO 2 + TiO 2 + ZrO 2) or less. If it exceeds 6% by mass, the meltability of the glass is lowered, and the glass becomes unstable during production. The upper limit of the content is more preferably 5% by mass or less, and still more preferably not contained.

CeO 2 acts as an oxidant in the glass composition, and is therefore a component that acts as a de-buying accelerator when used as a glass paste, press frit, or green sheet, but is not an essential component. The content is preferably 1% by mass or less. SnO 2 , TiO 2, and ZrO 2 act as crystal nuclei during firing, but have low solubility in molten glass. Therefore, the content is preferably 6% by mass or less. Since SnO 2 has a particularly low solubility in molten glass, it is more preferably 1% by mass or less. However, SnO 2 is a metal oxide that is easily reduced, and may be metallized in a reducing atmosphere.

The total amount of MgO + ZnO + La 2 O 3 is preferably 45 to 60 mol%. It affects the flowability of the glass powder during firing, the crystallinity of the fired body, and the degree of bending of the linear expansion curve of the fired body. Among these, compared to other glass components, it is a component that particularly affects the degree of bending, and in the present invention, it has been found that there is a correlation as shown in FIG. That is, if it is less than 45 mol%, the degree of crystallinity decreases and the degree of bending of the linear expansion curve increases. On the other hand, if it exceeds 60 mol%, the degree of bending becomes small, but the glass powder cannot obtain the desired fluidity during firing. Therefore, content is a total amount, 46 to 59 mol% is more preferable, 50 to 57 mol% is further more preferable.

  The glass composition of the present invention contains substantially no alkali metal. In the present specification, the phrase “substantially not containing an alkali metal” means that it contains no impurities other than unavoidable impurities.

In addition to the metal oxide, Y 2 O 3 is preferably contained. On the other hand, since Y 2 O 3 has a property of suppressing the degree of crystallinity, it is preferably used when it is desired to reduce the crystallization speed during firing. At that time, the content of Y 2 O 3 is preferably 3 to 5% by mass.

  Next, the sealing material of this invention produced from the glass composition of this invention is demonstrated.

  The sealing material of this invention can be used for sealing of sealing materials, such as a metal and ceramics, as a sintered body. Examples of the sealing form include metal and metal, metal and ceramic, or ceramic and ceramic. In particular, it is preferably used for sealing a sealing material having a linear expansion coefficient comparable to that of the fired body after firing.

  Examples of the sealing material include glass frit made of glass powder produced from the glass composition of the present invention, or glass paste, press frit, or green sheet produced from the glass frit. The glass frit is produced by removing particles having a particle size of 300 μm or more from glass powder obtained by pulverizing a glass composition. And a sealing material is properly used as needed.

  In the sealing material, a refractory filler having a melting point or a softening point of 1000 ° C. or more may be added for the purpose of adjusting the fluidity or the linear expansion coefficient within a range not impairing the function of the present invention. Examples of the refractory filler include tetragonal zirconia, magnesia, forsterite, enstatite, and diopsite partially stabilized with alumina, yttria and the like. And it is preferable that the addition amount shall be 80-99 volume% of glass powder and 1-20 volume% of filler in the total volume of glass powder and a filler. If the added amount of the filler is less than 1% by volume, the effect is not sufficiently exhibited, and if it exceeds 20% by volume, the fluidity of the glass powder is impaired during firing, which is not preferable.

  The glass paste of the present invention is produced by mixing the glass frit and an organic vehicle to form a paste. The organic vehicle used for the glass paste is preferably one in which a binder such as ethyl cellulose is dissolved in an organic solvent such as α-terpineol.

The press frit of the present invention is produced by putting a desired amount of the glass frit into a mold, press-molding at a pressure of 5 to 50 × 10 4 kPa, firing and firing for 10 to 120 minutes. The firing temperature is such that the press frit is deformed by firing at a temperature between the third bending point and the fourth bending point indicated by DTA so that the molded shape does not deform due to softening of the glass or the like. Can be fired without any problems.

  The green sheet of the present invention is produced by mixing the glass frit and an organic vehicle into a slurry, applying the slurry onto a transparent resin film using a doctor blade or the like, and drying. As said organic vehicle used for preparation of a green sheet, what melt | dissolved binders, such as butyral resin, in organic solvents, such as toluene, is preferable. The transparent resin film is preferably a sheet having releasability such as a PET film.

The sealing material of the present invention is suitable as a sealing material for SOFC. A sealing material is applied to the surface of the ceramic member and metal member constituting the seal, and fired to seal a desired component. And when using as a sealing material of SOFC, it is preferable that the linear expansion coefficient of a sintered body is the same as that of a sealing material, or a little low. As an SOFC sealing material, for example, cubic zirconia stabilized with Y 2 O 3 used as an electrolyte (YSZ, α = 100 × 10 −7 / ° C.), SUS430 used for a fuel manifold (α = 120) × 10 −7 / ° C.), excellent in thermal conductivity and insulation, expected as MgO (α = 130 × 10 −7 / ° C.) and a low-temperature operating electrolyte suitable for an electrolyte support and insulating layer And ceria (α = about 120 × 10 −7 / ° C.) to which gadolinium or the like is added.

  The glass frit, glass paste, press frit, and green sheet, which are the sealing materials of the present invention, are adjusted to have a low CaO content, have good flowability when the glass powder is fired, and bend the fired body. Since the degree is small, the occurrence of cracks inside the interface with the sealing material can be suppressed when sealing. Therefore, cracking hardly occurs at the sealing portion, and the durability of insulation and airtightness is excellent.

Specific embodiments of the present invention will be described below, but the present invention is not limited thereto. Here, Examples 3, 4 , and 6 to 11 in Tables 1 to 6 are examples, Examples 1 , 2 , and 5 are reference examples, and Examples 12 to 17 are comparative examples. Tables 1 to 3 show the glass composition in mass%, and Tables 4 to 6 show the glass composition in mol%, respectively.

  Glass raw materials were prepared and mixed so as to have the composition of Examples 1 to 17, and melted for 1.5 hours using a platinum crucible in an electric furnace at 1450 to 1500 ° C., and a thin glass sheet using two twin rollers. Then, it was molded and cooled to obtain a glass composition. This was pulverized with a ball mill (trade name: HD-B-105, manufactured by Nikkato Co., Ltd.) until the average particle size was 10 to 15 μm and the maximum particle size was 150 μm or less, and then passed through a sieve of 100 mesh (aperture 150 μm). Thus, coarse particles were removed to prepare glass powder.

  About the obtained glass powder, fluidity | liquidity was investigated with the following method. The results are shown in Table 1.

(Liquidity)
A powder mold of φ15 mm was filled with 1.5 g glass frit, and a compacted sample was prepared by a hand press with a weight of 1.47 kN. This sample was fired on SUS430 and evaluated for fluidity. A green compact that did not retain its cylindrical shape was marked with “◯”, and a cylindrical shape with left corners was marked with “X”.

  The glass powder produced by the above-mentioned method was heated from room temperature to 800 ° C. or 850 ° C. at 200 ° C./hour, kept at 800 ° C. or 850 ° C. for 1 hour, then cooled to room temperature at 600 ° C./hour, A fired body of glass powder was obtained.

  The obtained sintered body was examined for yield temperature, linear expansion coefficient, linear expansion curve, and bending degree calculated therefrom. Further, the glass powder was fired on the SUS430 substrate, and the corrosivity of the fired substrate and the occurrence of cracks at the adhesive interface were examined. Table 1 shows the yield temperature, the average linear expansion coefficient (α), the degree of bending, and the metal corrosivity. Table 3 shows the results of the occurrence of cracks.

(Bending temperature)
The yield temperature (unit: ° C.) of the fired body produced with the above temperature profile was measured using a differential thermal analyzer.
A sample obtained by polishing the produced fired body into a cylindrical shape of φ5 mm × 20 mm was measured with a thermomechanical analyzer (trade name: Thermoplus 2 system TMA8310, manufactured by RIGAKU). Heating was performed from room temperature to 900 ° C. or 1000 ° C. under a load of 10 g and 10 ° C./min, and the temperature at which the shrinkage amount was 5 μm or more was defined as the yield temperature.

(Linear expansion coefficient)
Similar to the yield temperature, a sample polished in a cylindrical shape of φ5 mm × 20 mm was used and measured with a thermomechanical analyzer (trade name: Thermoplus 2 system TMA8310, manufactured by RIGAKU). A linear expansion coefficient of 50 to 800 ° C. is obtained from a linear expansion curve obtained when the temperature is increased from room temperature to 900 ° C. or 1000 ° C. under a condition of 10 ° C./min with a weight of 10 g, and a line of 50 to 800 ° C. is obtained therefrom. The average value of the expansion coefficient was calculated.

(Bending degree)
From the linear expansion coefficient measurement results, the linear expansion coefficient based on 50 ° C. was calculated every 300 ° C. at 300 to 1000 ° C. And the maximum value of the difference of the linear expansion coefficient between adjacent 100 degreeC was made into the bending degree.

(Corrosive)
The appearance of the end faces of the SUS430 and the glass sample of the fired body obtained by the fluidity evaluation was visually observed. On SUS430, the case where the deteriorated layer that was not seen before firing was not seen was “◯”, and the case where it was seen was “x”. In addition, the thing which is not measured is set to "-".

(Occurrence of cracks)
The SUS430 and the glass sample of the fired body obtained by the fluidity evaluation were peeled, and the appearance of the adhesion surface of the SUS430 and the fired body was visually observed. The results are shown in Table 7.

  The sealing material containing the glass composition of the present invention as a main component can be brought into contact with the sealing material, fired at less than 900 ° C., and sealed. The fired body obtained by firing the glass powder of the glass composition of the present invention does not deform at 600 to 1000 degrees and is suitable for sealing a portion exposed to a high temperature. In particular, it can be used as a sealing material suitable for a SOFC seal.

Claims (10)

  1. It contains substantially no alkali metal oxide and is expressed in mass% in terms of oxide.
    SiO 2 2~30% by weight,
    B 2 O 3 10 to 30 wt%,
    MgO 5 to 35% by mass,
    Exceeding 10% by mass exceeding Al 2 O 3 0,
    ZnO 0-25% by mass,
    BaO 0-30% by mass,
    La 2 O 3 6~45 wt%,
    MO 2 0-6 mass% (M is one or more elements selected from the group consisting of Ce, Sn, Zr and Ti),
    Glass frit, characterized in that it consists essentially Iga Las composition containing CaO.
  2. The sintered body of the glass frit, the average linear expansion coefficient (alpha) is at 50 to 800 ° C., a glass frit according to claim 1, wherein the 90~135 × 10 -7 / ℃.
  3. The fired body of the glass frit according to claim 1 .
  4. The average linear expansion coefficient (α) at 50 to 800 ° C. is 90 to 135 × 10 -7 The fired body according to claim 3, which is / ° C.
  5. A glass paste comprising the glass frit according to claim 1 or 2 and an organic vehicle.
  6. A press frit comprising the glass frit according to claim 1 .
  7. A green sheet comprising the glass frit according to claim 1 .
  8. A sealing material for a solid oxide fuel cell, wherein the glass frit according to claim 1 or 2 is used.
  9. It contains substantially no alkali metal oxide and is expressed in mass% in terms of oxide.
    SiO 2   2-30% by mass,
    B 2 O 3   10-30% by mass,
    MgO 5 to 35% by mass,
    Al 2 O 3   More than 0 and 10% by mass or less,
    ZnO 0-25% by mass,
    BaO 0-30% by mass,
    La 2 O 3   6-45% by mass,
    MO 2   0 to 6% by mass (M is one or more elements selected from the group consisting of Ce, Sn, Zr and Ti),
    A crystallized glass characterized by having a glass composition substantially free of CaO.
  10. The average linear expansion coefficient ((alpha)) in 50-800 degreeC is 90-135 * 10 < -7 > / degreeC , Crystallized glass of Claim 9 characterized by the above-mentioned .
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